Parasiticide derived from terpenes



V Patented Nov. 25, 1941 9 UNITED STATES I PATENT OFFICE 2,263,716PARASITI CIDE DERIVED FROM TEBPENES Joseph N. Borglin, Wilmington, DeL,assignor to Hercules Powder Company, Wilmington, Del.,. a corporation ofDelaware No Drawing. Application March 29, 1940,"

' Serial N0. 326,658

6 Claims. (01. 167-30) tellurium.

I'have found that these compounds, the terpene ether thiocyanates, theterpene ether selenocyanates, and terpene ether tellurocyanates, areexceedingly effective parasiticides either when used alone or dilutedwith other toxic materials or with carriers. Furthermore, I have foundthat, strangely enough, they are definitely more effective parasiticidesthan the corresponding alkyl compounds heretofore used for this purpose.The various thio-, seleno-, and tellurocyanates of the terpene ethersare particularly useful as insecticides and especially as contactinsecticides against insects such as aphids, flies, roaches, bedbugs,fleas, etc., and are useful in the control of fungi or othermicro-organisms.

The composition inaccordance with this invention will comprise acompound of the type formula, R-(CNX), in which R is a radical of aterpene ether and X is an element of the group consisting of sulfur,selenium, and tellurium, and the (CNX) is linked to a carbon atom in theterpene nucleus. As will be apparent from the method of preparation, theterpene ether radical may be derived from such terpene ethers as, forexample, terpinyl ethers of methyl, ethyl, propyl, butyl, phenyl,lauryl, oleyl, stearyl, furfuryl, etc. alcohols; or such ethers as theterpinyl ethers of ethylene glycol, glycerol, triethylene glycol,nitroisopropyl glycol, monoethyl ether of ethylene glycol, monoordiethyl ether of glycerol, glycol monoacetate, glycerol dipropionate,etc. Similar ethers derived from otherterpene radicals such as areformed by the reaction of alcohols of the nature of those mentioned withdipentene, terpinene, terpinolene, borneol, fenchyl alcohol, etc. mayalso serve as the terpene ether base from which the thiocyanates,selenocyanates, and tellurocyanates utilized according to this inventionmay be derived.

The thiocyanates, selenocyanates, and telluromethods of preparation anunsaturated terpene ether is reacted with thiocyanogen, ,selenocyanogen,or tellurocyanogen, conveniently at room temperature, and recovering thereaction product; or a terpene ether mercaptide' prepared, for example,by the reaction of a terpene'ether mercaptan with a metal salt such aslead acetate, copper acetate, etc., is reacted with a cyanogen halide.Examples of the preparation of thiocyanates of .terpene ethers follow.All parts and percentages herein are by weight.

EXAMPLE I Preparation of thiocyanate of terpt'nylmethyl ether Thethiocyanate of a terpinylmethyl ether (the ether prepared by theaddition of methanol to pinene in the presence of sulfuric acid), wasprepared by adding parts by weight of lead thiocyanate to 250 parts byweight of glacial acetic acid and 25 parts by weight of bromine. Whenthe bromine had completely reacted, 50 parts by 7 weight ofterpinylmethyl ether was slowly added and the solution allowed to standovernight. It was then filtered, the filtrate washed with water toremove the acetic acid, and the recovered product dried. The productanalyzed 9.2% sulfur showing it to contain of the desired thiocyanate.

EXAMPLE II Preparation of thiocyanate of ethyleneglycol ether ofdipentene The thiocyanate of dipentene ethyleneglycol ether (the etherprepared by the addition of ethyleneglycol to dipentene in the presenceof sulfuric acid) was prepared by adding 41.7 parts by weight of leadthiocyanate to parts by weight of glacial acetic acid and then addingslowly 19.5 parts by weight of bromine. After the solution had stood for1 hour with intermitcyanates of the terpene ethers may be prepared bythe method disclosed in U. S. Patent 2,188,495

March 18, 1938. In accordance with these tent shaking, 30 parts of thedipentene ether of ethyleneglycol was added slowly with agitation andexternal cooling of the reaction mixture. The reaction mixture wasallowed to stand overnight, then filtered, the filtrate washed withwater to remove the acetic acid, and the recovered product (28 parts)dried. The product analyzed 7.0% sulfur.

yvashed until acid free.

Exams: III

Preparation of the thiocllanate of the nitroisobutul ether of eampheneThe thiocyanate of the nitroisobutyl ether of camphene (ether preparedby the addition oinitroisobutyl alcohol to camphene in the presence of85% phosphoric acid) was prepared by slowly adding 25 parts by weight ofbromine to 65 parts by weight of lead thiocyanate suspended in 250 partsby weight of glacial acetic acid; allowing the mixture to stand withintermittent shaking until the color of bromine had disappeared, andthen slowly adding 74 parts by weight of camphene nitroisobutyl etherand allowing the mixture to stand for three days at room temperature.The precipitated salts were filtered oil and about 100 parts ofpetroleum ether added to the filtrate, which was then water solvent bybubbling air through the solution under reduced pressure, 47 parts ofthe halocyanate of camphene (isobornyl) nitroisobutyl ether wasobtained. It analyzed 2.3% sulfur.

Emmett: ll' i Preparation of the thiocyaraate or terpinylpropyl etherForty parts by weight of terplnylpropyl ether mercaptan prepared by themethod described in U. 8. Patent 2,076,875 was converted to the leadPreparation of the thiocyanute of terzn'nyZ-nitroisobutyi ether Fortyparts by weight of terpinyl-nitroisobutyl ether mercaptan prepared bythe method described in the U. S. Patent 2,076,875 was converted to thelead mercaptide by mixing it with an excess oi an aqueous solution oflead acetate. An ether solution of the terpene nitroisobutyl ether leadmercaptide was then added to an ethyl alcohol solution of cyanogenbromide and lead bromide precipitated. The filtered solution was thenwashed with water and the solvent evaporated to recover the thiocyanateof terpene nitroisobutyl ether.

, The parasiticide according to this invention will usually comprise athiocyanate, selenocyanate, or tellurocyanate of a terpene ether and aninert carrier material or diluent. It may also contain a diluent orcarrier material which may be another toxic material or an admixture oftoxic materials, or it may contain such additional Upon removal or thesuch as, for example, water, petroleum hydrocarbons, etc., as ordinaryor deodorized kerosene,

' mineral oils, as, white oil, etc. The carrier used in compositionsintended for application as a dust will be a finely divided solid of thetype commonly used as a carrier for insecticidal dusts such as, forexample, talc, colloidal clays, bentonite, fullers earth, sulfur, etc.

toxic material or materials and an inert diluent.

Compositions for application as a spray may be utilized in the form of asolution or suspension. Such suitable solutions will comprise a terpeneether thiocyanate, a terpene ether selenocyanate, or terpene ethertellurocyanate or an admixture of these materials dissolved in a carrierliquid which is a solvent thereof, such as, for example, deodorized orordinary kerosene, mineral oils, as, white 011, etc. Such compositionsare suitable for use in the control of insects, such as, flies,mosquitoes, roaches, bed bugs, fleas, silver fish, etc.

A typical composition of this type for spray I application will consistof a terpene ether thiocyanate, terpene ether selenocyanate, or terpeneether tellurocyanate in kerosene, the terpene ether derivative being inan amount within the range of about 0.1% to about 10% by weight, of thecomposition. Concentrates for dilution to produce compositions oi thistype will carry higher concentrations of a terpene ether thiccyanate,terpene ether selenocyanate, or terpene ether tellurocyanate.

Compositions for application as a spray may I also be utilized in theform of an aqueous emulsion. Such compositions will comprise athincyanate, selenocyanate, or tellurocyanate derivative of a terpeneether which may be either emulsified directly in water, or dissolved ina limited amount of a water-immiscible solvent and the solution thusformed'emulsified in water. Such emulsions will desirably containemulsifying agents such as, for example, a soap, 2. sulfonated oil,salts of sulfated fatty or resin alcohols, etc. They may be prepared incompletely finished form at the point of manufacture or they may beprepared in the form of a concentrate com prising the terpene derivativeand an emulsifying agent, and then diluted and emulsified with water atthe point of application, thus, avoiding the packaging, transportationand handling of water. 'Emulsifled compositions of this type areadvantageous for the destruction of insects attacking horticulturalplants such as, for example, the various kinds of plant lice, harlequin,cabbage bugs, canker worms, thrips, aphids, Japanese beetles, Mexicanbean beetles, etc.

The insecticidal compositions in accordance with this invention may alsobe used in the form of insecticidal dust for the destruction of insectswhich attack agricultural or horticultural plants and other insects. Theterpene ether thiocyahates, selenocyanates, or tellurocyanates, eitheralone or admixed with other toxic insecticidal materials, will bethoroughly admixed with a powdered solid material of the type commonlyused for insecticidal dusts to produce such an insecticidal dust.

A typical composition of this type is, for example, talc, ground to 200mesh and incorporating from about 1% to about 10% by weight,

- tellurocyanate.

Thiocyanate oi terpene nitroisobutyl This application is acontinuation-in-part of my application entitled Terpene thiocyanateinsecticides, Serial No. 207,779, filed May 13, 1938.

ether 'lhlocyanate oi dipentene methyl ether.

Deodoflieed kerosene.-

Rotenone Table I Ingredients I H III IV V VI VII VIII IX X XI XII Per-Per- Per- Per- Per- Per- Per- Per Per- Per- Per- Percent cent cent centcent cent cent cent cent cent cent Thlocyanate of terplnyl glycoletheL... 3 2 2 2 10 Examples of insecticidal powder in accordance withthis invention are shown in Table II which follows:

Table II XIII XIV XV Percent Percent Percent Terpene ether thiocyanate10 25 Pulverized suliur 5 75 r Kieselguhr--. 85 75 The compositions inaccordance with this invention are further illustrated, and their hightoxicity shown, by the data set forth in Table III By parasiticideherein and in the claims is meant a composition intended to kill insectsand other insect-like pestiterous animals and also undesiredmicro-organisms.

It will be understood that the details and examples given herein are byway of illustration and not by way of limitation of the -invention asbroadly described and claimed.

What-I claim and desire to protect by Letters Patent is:

1. A paresiticide comprising a compound of the formula RPCNX in which Ris a terpene ether, X is an element selected from the group consistingot sulfur, selenium, and tellurium and the CNX radical is directlyattached to a carbon atom of the terpene portion of the terpene ether.

2. A parasiticide comprising a compound of the formula R-CNS in which Ris a. terpene ether and in which the CNS group is directly attached to acarbon atom of the terpene portion or the terpene ether.

3. A parasiticide comprising a thiocyanate of an ether or pinene inwhich the thiocyanate group is directly attached to a carbon atom of theterpene portion of the terpene ether.

4. A parasiticide comprising terpinyl methyl eth'er thiocyanate, thethiocyanate group being directly attached to a. terpene carbon atom.

5. A parasiticide comprising terpinyl ethyl ether thiocyanate, thethiocyanate group being directly attached to a terpene carbon atom 6. Aparasiticide comprising terpinyl glyceryl ether thiocyanate, thethiocyanate group being dlrectlyattached to a terpene carbon atom.

JOSEPH N. BORGIJN.

